Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
  • C08F222/10—Esters
  • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
  • C08F222/106—Esters of polycondensation macromers
  • C08F222/1065—Esters of polycondensation macromers of alcohol terminated (poly)urethanes, e.g. urethane(meth)acrylates
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
  • C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B33—ADDITIVE MANUFACTURING TECHNOLOGY
  • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
  • B33Y10/00—Processes of additive manufacturing
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B33—ADDITIVE MANUFACTURING TECHNOLOGY
  • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
  • B33Y70/00—Materials specially adapted for additive manufacturing
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2/00—Processes of polymerisation
  • C08F2/46—Polymerisation initiated by wave energy or particle radiation
  • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/12—Esters of monohydric alcohols or phenols
  • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
  • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
  • C08F220/1811—C10or C11-(Meth)acrylate, e.g. isodecyl (meth)acrylate, isobornyl (meth)acrylate or 2-naphthyl (meth)acrylate
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
  • C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
  • C08F220/281—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing only one oxygen, e.g. furfuryl (meth)acrylate or 2-methoxyethyl (meth)acrylate
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
  • C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
  • C08F220/282—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing two or more oxygen atoms
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
  • C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
  • C08F220/283—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing one or more carboxylic moiety in the chain, e.g. acetoacetoxyethyl(meth)acrylate
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/14—Peroxides
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/49—Phosphorus-containing compounds
  • C08K5/51—Phosphorus bound to oxygen
  • C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
  • C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
  • C08L33/04—Homopolymers or copolymers of esters
  • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
  • C08L33/04—Homopolymers or copolymers of esters
  • C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2312/00—Crosslinking
  • C08L2312/06—Crosslinking by radiation

Definitions

• Crosslinkable composition comprising a mono (meth) acrylate having a 1,3-dioxolane ring
• the present invention relates to a crosslinkable composition
• a crosslinkable composition comprising a mono (meth) acrylate comprising a 1,3-dioxolane ring, another mono (meth) acrylate as well as a (meth) acrylated oligomer.
• the invention also relates to a process for the manufacture of a crosslinked product, in particular of a 3D object, from this composition as well as the use of this composition for obtaining an ink, a coating, sealant, adhesive, molded material, ink pad, or 3D object.
• the invention further relates to the use of a mono (meth) acrylate having a 1,3-dioxolane ring in a composition for 3D printing.
• compositions in particular the compositions crosslinkable by radiation, are commonly used to obtain inks, coatings as well as 3D objects.
• the compositions must exhibit advantageous properties in terms of viscosity, hardness, tensile strength and / or elasticity.
• the Applicant has selected a particular mono (meth) acrylate monomer, namely a mono (meth) acrylate having a 1,3-dioxolane ring, for its balanced properties.
• This monomer when it is combined with another mono (meth) acrylate and with a (meth) acrylated oligomer, in specific proportions, makes it possible to obtain crosslinkable compositions exhibiting advantageous properties in terms of viscosity, hardness, resistance to breakage and / or elasticity.
• These compositions are especially useful for obtaining an ink, a coating, a mastic, an adhesive, an inking plate or a molded material.
• the crosslinkable compositions can be used in 3D printing.
• Certain 3D printing techniques cause the printed object to undergo significant deformations. This is particularly the case for tank processes when the mobile platform rises gradually (“bottom-up” process). Indeed, the successive layers of the object are subjected to adhesion forces that must be broken when lifting the object under construction to move on to the next layer, in particular the suction effect between the printed layer and the bottom of the tank.
• this suction effect between the printed layer and the bottom of the tank can destroy the newly formed layer which remains fragile .
• the crosslinkable composition By varying the soft / hard and / or hydrophilic / hydrophobic character of the mono (meth) acrylate which is combined with the mono (meth) acrylate having a 1,3-dioxolane ring, it is possible to use the crosslinkable composition in the Most 3D printing techniques, including tank printing or inkjet printing, in order to obtain 3D objects with advantageous mechanical properties. In particular, it is possible to obtain flexible and / or elastomeric 3D objects.
• a subject of the invention is thus a composition
• a composition comprising: a) 5 to less than 50%, in particular 10 to 40%, more particularly 15 to 30%, of a component A) which is a mono (meth) acrylate comprising a 1,3-dioxolane ring; b) 10 to 75%, in particular 15 to 70%, more particularly 20 to 60%, of a component B) which is a mono (meth) acrylate distinct from A); c) 0 to less than 45%, in particular 1 to 40%, more particularly 2 to 20%, of a component C) which is a di (meth) acrylate having a weight average molecular mass Mw less than or equal to 650 g / mol; d) 0 to 30%, in particular 0 to 20%, of a component D) which is a tri (meth) acrylate having a weight average molecular mass Mw of less than or equal to 600 g / mol; e) 0 to 30%, in particular 0 to 20%,
• a subject of the invention is also a process for the manufacture of a crosslinked product, the process comprising the crosslinking of the composition according to the invention, in particular by exposing the composition to radiation, more particularly to UV rays, near UV. , visible, infrared or near-infrared or to an electron beam.
• radiation more particularly to UV rays, near UV. , visible, infrared or near-infrared or to an electron beam.
• the invention also relates to a process for the manufacture of a 3D object, comprising printing a 3D object using the composition according to the invention; in particular the printing of a 3D object continuously or layer by layer.
• Another subject of the invention is a crosslinked product obtained by crosslinking the composition according to the invention or obtained by implementing the process according to the invention.
• the invention also relates to the use of the composition according to the invention for obtaining an ink, a coating, a mastic, an adhesive, a molded material, a ink plate or a 3D object, in particular a 3D object.
• Another object of the invention is the use of a mono (meth) acrylate comprising a 1,3-dioxolane ring in a composition for 3D printing.
• 1,3-dioxolane means a ring of 5 atoms including two oxygen atoms, the two oxygen atoms being separated by a carbon atom.
• (meth) acrylate means acrylate or methacrylate.
• the (meth) acrylate is an acrylate.
• mono (meth) acrylate means a compound having a single (meth) acrylate group. In particular, mono (meth) acrylate is a monoacrylate having a single acrylate group.
• di (meth) acrylate means a compound having two (meth) acrylate groups.
• di (meth) acrylate is a diacrylate having two acrylate groups.
• tri (meth) acrylate means a compound having three (meth) acrylate groups.
• tri (meth) acrylate is a triacrylate having three acrylate groups.
• tetra (meth) acrylate means a compound having four (meth) acrylate groups.
• tetra (meth) acrylate is a tetraacrylate having four acrylate groups.
• alkyl means a monovalent saturated acyclic hydrocarbon radical of formula -C n f i.
• Alkyl can be linear or branched.
• a "C1-C6 alkyl” means an alkyl comprising 1 to 6 carbon atoms. Examples of alkyl groups are methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl and hexyl.
• cycloalkyl means a monovalent saturated hydrocarbon radical comprising a ring.
• a "C5-C12 cycloalkyl” means a cycloalkyl comprising 5 to 12 carbon atoms. Examples of cycloalkyl groups are cyclopentyl, cyclohexyl and isobornyl.
• alkylaryl means an alkyl substituted with an aromatic group such as a phenyl group.
• An example of an alkylaryl is the benzyl group (-Chh-Phenyl).
• alkylene means a divalent saturated acyclic hydrocarbon radical of formula -C n H2 n - An alkylene may be linear or branched.
• a "C1-C12 alkylene” means an alkylene comprising 1 to 12 carbon atoms.
• oxyalkylene means a divalent group having one or more -OC n hh n - units with n ranging from 2 to 4.
• polyol means a compound comprising at least two hydroxyl functions.
• the functionality of a polyol is the number of hydroxyl functions it contains.
• polyester means a compound comprising at least two ester bonds.
• polyether means a compound comprising at least two ether linkages.
• polycarbonate means a compound comprising at least two carbonate bonds.
• polyester polyol means a polyester comprising at least two hydroxyl functions.
• polyether polyol means a polyether comprising at least two hydroxyl functions.
• polycarbonate polyol means a polycarbonate comprising at least two hydroxyl functions.
• hydrocarbon chain means a chain comprising only carbon and hydrogen atoms. Unless stated otherwise, a hydrocarbon chain is not substituted or interrupted by a heteroatom.
• a hydrocarbon chain can be linear or branched, saturated or unsaturated, aliphatic, cycloaliphatic or aromatic.
• a “C4-C24 hydrocarbon chain” is a hydrocarbon chain comprising 4 to 24 carbon atoms.
• hydroxyl function means an —OH function
• carboxylic acid function means a -COOH function
• ether bond means an -O- bond.
• a “soft” compound means a compound having a Tg of -100 to 24 ° C.
• a “hard” compound means a compound having a Tg of 25-200 ° C.
• the Tg of a monomer can in particular be measured on the corresponding homopolymer according to the method described below.
• a hydrophilic mono (meth) acrylate means a mono (meth) acrylate comprising one or more oxygen and / or nitrogen atoms in addition to the oxygen atoms contained in the (meth) acrylate group.
• a hydrophilic mono (meth) acrylate can in particular have Hansen solubility parameters dr and ôh corresponding to the following equation:
• a mono (meth) acrylate hydrophilic can comprise an element selected from a hydroxyl group (-OH), a primary or secondary amino group (-NH2 or -NH (C1-C6 alkyl)), an alkoxylated chain (comprising at least one unit - [0- ( C1-C6 alkylene)] -), an oxygenated or nitrogenous heterocycle, a urethane function, a urea function, an ester function, an amide function, a carboxylic acid function, an ether function, a carbonate function and mixtures thereof.
• hydrophobic mono (meth) acrylate means a mono (meth) acrylate having no nitrogen atom or oxygen atom other than the oxygen atoms contained in the (meth) acrylate group.
• a hydrophobic mono (meth) acrylate can in particular have Hansen solubility parameters dr and 5h corresponding to the following equation: ôh ⁇ 30.5 - 2.2 * dr.
• a hydrophobic mono (meth) acrylate can comprise an element chosen from a C4-C24 hydrocarbon chain.
• ethylenically unsaturated means a compound comprising a polymerizable carbon-carbon double bond.
• a polymerizable carbon-carbon double bond is a carbon-carbon double bond that can react with another carbon-carbon double bond in a polymerization reaction.
• Carbon-carbon double bonds in a phenyl ring are not considered polymerizable carbon-carbon double bonds.
• polyisocyanate means a compound having at least two isocyanate functions.
• cycloaliphatic means a non-aromatic cyclic compound. It can be substituted by one or more groups / functions as defined for the term “Aliphatic”. It can comprise one or more bonds / functions as defined for the term “aliphatic”.
• aromatic means a compound comprising an aromatic ring, that is to say complying with Hückel's rule of aromaticity, in particular a compound comprising a phenyl group. It can be substituted by one or more groups / functions as defined for the term “aliphatic”. It can comprise one or more bonds / functions as defined for the term “aliphatic”.
• saturated means a compound which does not include a carbon-carbon double or triple bond.
• unsaturated means a compound which comprises a carbon-carbon double or triple bond, in particular a carbon-carbon double bond.
• polycarboxylic acid means a compound comprising at least two carboxylic acid functions.
• 3D object means a three-dimensional object obtained by 3D printing.
• ink plate means a relief plate intended for printing, especially in flexography.
• composition according to the invention comprises a component A).
• the composition can comprise a mixture of components A).
• Component A) is a mono (meth) acrylate comprising a 1,3-dioxolane ring.
• component A) is a monoacrylate comprising a 1,3-dioxolane ring.
• Component A) can in particular correspond to the following formula (I):
• R1 and R2 are independently selected from H, C1-C6 alkyl, C5-C12 cycloalkyl and alkylaryl;
• R 3 , R 4 , Rs and R 6 are independently H or methyl; n is 1, 2, 3, 4 or 5.
• R 1 and R 2 can be independently selected from H, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, cyclohexyl, isobornyl and benzyl.
• R 1 and R 2 are independently selected from H, methyl and ethyl. More particularly, R 1 and R 2 are methyl.
• R 3 , R4 and Rs are H.
• Re can be H or methyl.
• Re is H.
• n 1
• component A) corresponds to formula (I) above in which R 1 and R 2 are independently chosen from H, methyl and ethyl, preferably R 1 and R 2 are methyl;
• Re is H or methyl, preferably Re is H; n is 1.
• Suitable examples of component A) are (2,2-dimethyl-1, 3-dioxolan-4-yl) methyl acrylate, (2-ethyl-2-methyl-1,3-dioxolan-4 -yl) methyl acrylate and glycerol formaldehyde methacrylate.
• component A) is (2,2-dimethyl-1,3-dioxolan-4-yl) methyl acrylate represented by the following formula (Ia):
• composition according to the invention comprises 5 to less than 50%, in particular 10 to 40%, more particularly 15 to 30%, by weight of component A) relative to the weight of all of the components A) to I).
• Component B) The composition according to the invention comprises a component B).
• the composition can comprise a mixture of components B).
• the composition comprises one, two or three distinct components B).
• Component B) is a mono (meth) acrylate distinct from component A).
• component B) is a monoacrylate distinct from component A).
• Component B) can in particular correspond to the following formula (II): in which
• R7 is the residue of a monoalcohol or polyol chosen from a monoalcohol or polyol of polyether type, a monoalcohol or polyol of polyester type, a monoalcohol or polyol of polycarbonate type, a monoalcohol or aliphatic polyol, a monoalcohol or cycloaliphatic polyol, a monoalcohol or aromatic polyol, and the alkoxylated, in particular ethoxylated and / or propoxylated, derivatives of said monoalcohols or polyols;
• Rs is H or methyl, in particular Rs is H.
• Component B) can in particular be chosen from a soft and hydrophilic mono (meth) acrylate, a soft and hydrophobic mono (meth) acrylate, a hard and hydrophilic mono (meth) acrylate, a hard and hydrophobic mono (meth) acrylate and their mixtures.
• component B) comprises a soft and hydrophilic mono (meth) acrylate.
• Component B) can in particular comprise a mixture of soft and hydrophilic mono (meth) acrylates. More particularly, component B) can comprise a soft and hydrophilic mono (meth) acrylate chosen from 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, triethylene glycol monoacrylate, triethylene glycol monomethacrylate , polyethylene glycol monoacrylate, polyethylene glycol monomethacrylate, methoxypolyethylene glycol monoacrylate, methoxypolyethylene glycol monomethacrylate (in particular available under the references SR550 and SR552 from Arkema), polypropylene glycol monoacrylate, polypropylene glycol monomethacrylate (in particular available under the reference SR604 from Arkema) , 2-ethoxyethyl
• CTFA in particular available under the reference SR531 from Arkema
• 2 - [[(butylamino) carbonyl] oxy] ethyl acrylate in particular available under the reference Genomer® 1122 from Rahn
• mixtures thereof
• component B) comprises a soft and hydrophilic mono (meth) acrylate comprising a hydroxyl group, preferably a soft and hydrophilic monoacrylate comprising a hydroxyl group, more preferably a polycaprolactone monoacrylate.
• a polycaprolactone mono (meth) acrylate can in particular correspond to the following formula:
• L is alkylene or oxyalkylene, preferably L is - (CH 2 ) 2 - R 'is H or methyl, preferably R' is H; x is 1 to 10, preferably 1 to 6.
• component B) comprises a soft and hydrophobic mono (meth) acrylate. More particularly, component B) comprises a soft and hydrophobic mono (meth) acrylate chosen from octyl / decyl acrylate (in particular available under the reference SR484 from Arkema), / so-decyl acrylate (in particular available under the reference SR395 from 'Arkema), dodecyl acrylate (in particular available under the reference SR335 from Arkema), tridecyl acrylate (in particular available under the reference SR489 from Arkema), stearyl acrylate (in particular available under the reference SR586 from Arkema), behenyl acrylate (in particular available under the reference SR587 from Arkema), 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, butyl acrylate, butyl methacrylate, is
• component B) comprises a hard and hydrophilic mono (meth) acrylate. More particularly, component B) can comprise a hard and hydrophilic mono (meth) acrylate chosen from acrylic acid, 2- carboxyethyl acrylate, methacrylic acid, 2-hydroxypropyl methacrylate, 2-hydroxyethyl methacrylate, acryloyl morpholine, 2-phenoxyethyl methacrylate (in particular available under the reference SR340 from Arkema) and mixtures thereof.
• component B) comprises a hard and hydrophobic mono (meth) acrylate. More particularly, component B) comprises a hard and hydrophobic mono (meth) acrylate chosen from tert-butylcyclohexyl acrylate (in particular available under the reference SR217 from Arkema), tert-butylcyclohexyl methacrylate (in particular available under the reference SR218 from Arkema), trimethylcyclohexyl acrylate (in particular available under the reference SR420 from Arkema), trimethylcyclohexyl methacrylate (in particular available under the reference SR421A from Arkema), isobornyl acrylate (in particular available under the reference SR506D from Arkema), isobornyl methacrylate (in particular available under the reference SR423D from Arkema), ferf-butyl acrylate, ferf-butyl methacrylate, cyclohexyl acrylate
• component B) comprises a soft and hydrophilic mono (meth) acrylate optionally mixed with a hard and hydrophobic mono (meth) acrylate. More particularly, component B) comprises a soft and hydrophilic monoacrylate optionally in admixture with a hard and hydrophobic monoacrylate.
• component B) comprises at least 15% by weight, in particular 20 to 100%, more particularly 25 to 60%, by weight of soft and hydrophilic mono (meth) acrylate relative to the weight of component B).
• Component B) can in particular comprise a soft and hydrophilic monoacrylate comprising a hydroxyl group, in particular a polycaprolactone acrylate, optionally in admixture with a monoacrylate having a Tg greater than 40 ° C, in particular isobornyl acrylate.
• This embodiment is particularly suitable for a crosslinkable composition for obtaining flexible and / or elastomeric 3D objects.
• component B) can comprise a mono (meth) acrylate having a low surface tension.
• the surface tension can in particular be 20 to 35 mN / m, in particular 25 to 32 mN / m, as measured according to the method described below.
• Examples of mono (meth) acrylates having low surface tension are tert-butyl cyclohexyl acrylate, isobornyl acrylate, tricyclodecane methanol monoacrylate, isodecyl acrylate, 3, 5, 5-trimethylcyclohexyl acrylate, 3,5,5-trimethylcyclohexyl methacrylate, 2 -ethylhexyl acrylate, isooctyl acrylate, octyldecyl acrylate, tridecyl acrylate, lauryl acrylate, ethoxylated lauryl acrylate (4 ethoxy units), isodecyl methacrylate, tert-butylcyclohexyl methacrylate, isobornyl methacrylate, tricyclodecane methanol monomethacrylate and a C12-C15 alkyl methacrylate such as lauryl methacrylate. More particularly component B
• composition according to the invention comprises 10 to 75%, in particular 15 to 70%, more particularly 20 to 60%, by weight of component B) relative to the weight of all components A) to I).
• composition according to the invention can comprise a component C).
• the composition can comprise a mixture of components C).
• Component C) is a di (meth) acrylate.
• component C) is a diacrylate.
• Component C) has a weight average molecular mass Mw of less than or equal to 650 g / mol.
• component C) has an Mw of 100 to 600 g / mol, more particularly of 200 to 500 g / mol.
• Component C) can in particular correspond to the following formula (III): in which
• Rg is the residue of a polyol chosen from a polyether polyol, a polyester polyol, a polycarbonate polyol, an aliphatic polyol, a cycloaliphatic polyol, an aromatic polyol, a polybutadiene polyol, a polydialkylsiloxane polyol and alkoxylated derivatives, in particular ethoxylated and / or propoxylated, of said polyols;
• Rio and Ru are independently H or methyl, in particular Rio and Ru are H.
• Rg is the residue of a polyether polyol or of an optionally alkoxylated aliphatic polyol, in particular ethoxylated and / or propoxylated. More particularly Rg is the residue of a polyethylene glycol.
• a component C) having a polyether polyol residue can in particular correspond to the following formula (Ilia): (I Sla) wherein each R 12 is independently C2-C4 alkylene, in particular each f is independently ethylene, propylene or butylene;
• R13 and R14 are independently H or methyl, in particular R 13 and R 14 are H; m goes from 2 to 15.
• Component C) can in particular be a polyethylene glycol diacrylate corresponding to the formula (Ilia) in which R12 is an ethylene;
• R13 and R14 are H; m goes from 7 to 12, in particular m is 9.
• a component C) having an optionally alkoxylated aliphatic polyol residue can in particular correspond to the following formula (III b): wherein each R 15 and R 17 are independently C2-C4 alkylene, in particular each R 15 and R 17 are independently ethylene, propylene or butylene; R 16 is C1-C12 alkylene;
• Ris and R 19 are independently H or methyl, in particular Ris and R 19 are H; p and q, identical or different, go 0 to 10 and p + q go from 0 to 10.
• component C) corresponds to formula (III) in which
• Rg is the residue of a polyol selected from ethylene glycol,, 2-propanediol, 1,3-propanediol, 1, 4-butanediol, 1,3-butanediol, 1, 5-pentanediol, 1,6-hexanediol, 3- methyl-1, 5-pentanediol, 1, 10-decanediol, 1, 12-dodecanediol, diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, dibutylene glycol, tributylene glycol, a polyethylene glycol, a polypropylene glycol, a polybutylene glycol, 1, 4-cyclohexanedimethanol, 1, 6- cyclohexanedimethanol, 1, 4-cyclohexanediol, bisphenol A, hydrogenated bisphenol A, glycerol, diglycerol, a polyglycerol, tricyclo
• Rio and Ru are independently H or methyl, in particular Rio and Ru are H.
• composition according to the invention comprises 0 to less than 45%, in particular 1 to 40%, more particularly 2 to 20%, by weight of component C) relative to the weight of all components A) to I).
• composition according to the invention can comprise a component D).
• the composition can comprise a mixture of components D).
• Component D) is a tri (meth) acrylate.
• component D) is a triacrylate.
• Component D) has a weight average molecular mass Mw of less than or equal to 600 g / mol.
• component D) has an Mw of 100 to 550 g / mol, more particularly of 200 to 500 g / mol.
• Component D) can in particular correspond to the following formula (IV): in which
• R 20 is the residue of a polyether polyol or of an optionally alkoxylated aliphatic polyol, in particular ethoxylated and / or propoxylated, in particular R20 is the residue of a polyol chosen from trimethylolpropane, di (trimethylolpropane), trimethylolethane, 1,2 , 6-hexanetriol, 1,2,4-butanetriol, erythritol, pentaerythritol, di (pentaerythritol), glycerol, diglycerol, a polyglycerol, sorbitol, mannitol, xylitol, methyl glucoside, an isocyanurate, and alkoxylated derivatives, in particular ethoxylated and / or propoxylated, of said polyols;
• R21, R22 and R23 are independently H or methyl, in particular R21, R 22 and R 23 are H.
• the composition according to the invention comprises 0 to 30%, in particular 0 to 20%, by weight of component D) relative to the weight of all of the components A) to I).
• composition according to the invention can comprise a component E).
• the composition can comprise a mixture of components E).
• Component E) is a tetra (meth) acrylic late.
• component E) is a tetraacrylate.
• Component E) has a weight average molecular mass Mw of less than or equal to 600 g / mol.
• component E) has an Mw of 200 to 550 g / mol, more particularly of 300 to 500 g / mol.
• Component E) can in particular correspond to the following formula (V): in which
• R24 is the residue of an optionally alkoxylated aliphatic polyol, in particular ethoxylated and / or propoxylated, in particular R24 is the residue of a polyol chosen from di (trimethylolpropane), pentaerythritol, di (pentaerythritol) and alkoxylated derivatives, in particular ethoxylated and / or propoxylated, of said polyols;
• R25, R26, R27 and R28 are independently H or methyl, in particular R25, R26, R27 and R28 are H.
• the composition according to the invention comprises 0 to 30%, in particular 0 to 20%, by weight of component E) relative to the weight of all components A) to I).
• composition according to the invention comprises a component F).
• the composition can comprise a mixture of components F).
• Component F) is an oligomer comprising at least two (meth) acrylate groups.
• component F) is an oligomer comprising at least two acrylate groups.
• Component F) can in particular be an oligomer comprising 2 to 10, in particular 2 to 6, more particularly 2 to 4, (meth) acrylate groups.
• Component F) can in particular be an oligomer comprising 2 to 10, in particular 2 to 6, more particularly 2 to 4, acrylate groups.
• Component F) has a weight average molecular mass Mw greater than 700 g / mol.
• component F) has an Mw of 750 to 10,000 g / mol, more particularly of 1,000 to 3000 g / mol.
• Component F) can in particular be an oligomer chosen from a urethane (meth) acrylate, an epoxy (meth) acrylate, a polyether (meth) acrylate, a polyester (meth) acrylate.
• component F) is an oligomer chosen from a urethane acrylate, an epoxy acrylate, a polyether acrylate, a polyester acrylate and their mixtures.
• suitable epoxy (meth) acrylates include the reaction products of acrylic acid, methacrylic acid or a mixture thereof with an epoxy resin (polyglycidyl ether or ester).
• the epoxy resin can, in particular, be chosen from bisphenol A diglycidyl ether; bisphenol F diglycidyl ether; bisphenol S diglycidyl ether; bisphenol A diglycidyl brominated ether; bisphenol F diglycidyl brominated ether; bisphenol S diglycidyl brominated ether; hydrogenated bisphenol A diglycidyl ether; bisphenol F diglycidyl hydrogenated ether; hydrogenated bisphenol S diglycidyl ether; epoxy novolak resin; 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexanecarboxylate; 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane-1,4-di
• urethanes (meth) acrylates examples include urethanes based on aliphatic, cycloaliphatic and / or aromatic polyester polyols, polyether polyols or polycarbonate polyols and aliphatic, cycloaliphatic and / or diisocyanates. or aromatic.
• the urethanes (meth) acrylates can in particular be prepared by reacting an aliphatic, cycloaliphatic and / or aromatic polyisocyanate (for example a diisocyanate or triisocyanate) with a polyester polyol, polyether polyol, polycarbonate polyol, polycaprolactone polyol, polydimethysiloxane polyol or polyol, a mixture of these, to form an oligomer functionalized with isocyanate groups, which is then reacted with a (meth) acrylate comprising a hydroxy group, such as hydroxyethyl (meth) acrylate or hydroxypropyl (meth) acrylate, to introduce the (meth) acrylate groups.
• an aliphatic, cycloaliphatic and / or aromatic polyisocyanate for example a diisocyanate or triisocyanate
• a polyester polyol for example a diisocyanate or triis
• a (meth) acrylate comprising a hydroxy group can first react with a polyisocyanate to obtain an isocyanate functional (meth) acrylate, which is then reacted with a polyol.
• all reagents can react at the same time.
• polyester (meth) acrylates include reaction products of acrylic acid, methacrylic acid or a mixture thereof with a polyester polyol.
• the reaction can be carried out so that residual hydroxyl groups remain or else so that all the hydroxyl groups are (meth) acrylated.
• the polyester polyols can in particular be obtained by polycondensation between a polyol (for example a diol) and a polycarboxylic acid (for example a dicarboxylic acid or an anhydride).
• a polyester (meth) acrylate the hydroxyl groups of the polyester polyol are partially or totally esterified by reaction with (meth) acrylic acid, (meth) acryloyl chloride or (meth) acrylic anhydride.
• Polyesters (meth) acrylates can also be obtained by reacting a (meth) acrylate comprising a hydroxy group, such as hydroxyethyl (meth) acrylate or hydroxypropyl (meth) acrylate, with a polycarboxylic acid.
• Polyols and polycarboxylic acids can have linear or branched, aliphatic or aromatic, acyclic or cyclic structure.
• component F) is an aliphatic, cycloaliphatic or aromatic urethane diacrylate, more particularly an aliphatic urethane diacrylate.
• An example of a suitable aliphatic urethane diacrylate is available from Arkema under the reference CN966.
• polyether (meth) acrylates include reaction products of acrylic acid, methacrylic acid or a mixture thereof with a polyether polyol.
• Polyether polyols can be linear or branched. Polyether polyols can be obtained by ring-opening polymerization of epoxides (e.g. ethylene oxide, 1,2-propylene oxide or 1 -butene oxide) or other heterocyclic compounds containing oxygen (e.g. example oxetane or tetrahydofuran). Polyether polyols can also be obtained by condensation of diols, such as glycols.
• the oligomers described above can be modified with an amine or a thiol according to the procedures described in the literature.
• composition according to the invention comprises 5 to 80%, in particular 8 to 55%, more particularly 15 to 40%, by weight of component F) relative to the weight of all of the components A) to I).
• composition according to the invention can comprise a component G).
• the composition can comprise a mixture of components G).
• Component G) is an ethylenically unsaturated compound distinct from components A) through
• component G) can be a compound comprising from 1 to 10 ethylenically unsaturated groups chosen from acrylate, methacrylate, vinyl, allyl and their mixtures.
• Component G) can in particular be chosen from:
• N-vinyl compounds such as N-vinyl-pyrrolidone (NVP), N-vinyl-caprolactam (NVC), N-vinyl-imidazole, N-vinyl-N-methylacetamide (VI MA);
• O-vinyl compounds such as ethyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, tert-butyl vinyl ether, cyclohexyl vinyl ether (CHVE), 2-ethylhexyl vinyl ether (EHVE), dodecyl vinyl ether (DDVE) , octadecyl vinyl ether (ODVE), 1, 4-butanediol divinyl ether (BDDVE), diethylene glycol divinyl ether (DVE-2), triethylene glycol divinyl ether (DVE-3), 1, 4-cyclohexanedimethanol divinyl ether (CHDM-di)
• hydroxy vinyl compounds such as hydroxybutyl vinyl ether (HBVE), 1,4-cyclohexanedimethanol mono vinyl ether (CHDM-mono);
• TVCH 1, 2,4-trivinylcyclohexane
• VEEA 2- (2-vinyloxyethoxy) ethyl acrylate
• VEEM 2- (2-vinyloxyethoxy) ethyl methacrylate
• composition according to the invention comprises 0 to 30%, in particular 0 to 20%, by weight of component G) relative to the weight of all of the components A) to I).
• composition according to the invention can comprise a component H).
• the composition can comprise a mixture of components H).
• Component H) is an initiator.
• An initiator is a compound which generates radicals when heated and / or subjected to radiation and / or subjected to an oxidation-reduction reaction.
• the initiator is a peroxide.
• the composition according to the invention can be crosslinkable thermally or at low temperature in the presence of a peroxide reducing accelerator.
• the accelerator makes it possible in particular to accelerate the decomposition of peroxide at low temperature (in particular at room temperature: 20-25 ° C).
• the composition according to the invention can comprise a photoinitiator.
• a photoinitiator is an initiator that generates radicals when subjected to radiation.
• the composition according to the invention can be crosslinkable by radiation, in particular by UV, near UV, visible, infrared or near-infrared rays, by laser or by LED, preferably with a near UV-visible lamp.
• the wavelength range which corresponds to near UV-visible radiation is from 355 to 415 nm and that which corresponds to visible from 400 to 800 nm.
• the composition according to the invention does not include any initiator and in this case it can be crosslinkable by radiation with an electron beam.
• the composition according to the invention comprises a photoinitiator.
• the composition of the invention is crosslinkable by the dual route, which means that it combines at least two crosslinking techniques as defined above.
• dual routes under this alternative definition, we can cite the combination of a route based on the presence of a peroxide with that where at least one photoinitiator is present.
• the composition can be crosslinked either simultaneously or in successive stages by thermal or low temperature route in the presence of peroxide and by UV radiation route with the additional presence of a photoinitiator.
• rapid UV crosslinking in the presence of a photoinitiator can be followed by additional thermal crosslinking due to the presence of a peroxide with said photoinitiator, thus making it possible to complete / complete the crosslinking, in particular at a temperature greater than that of UV crosslinking.
• This may in particular be of interest when the glass transition temperature of the completely crosslinked composition is higher than that of the UV crosslinking temperature.
• a hydroperoxide R-O-O-H
• a dialkyl peroxide a diaryl peroxide or an aryl / alkyl peroxide
• R-O-O-R ’ a peroxyacid
• a peroxyester RC (O) -O-O-R '
• a diacyl peroxide RC (0) -0-0-C (0) -R ’
• a peroxyacetal a peroxycarbonate and mixtures thereof, R and R’ independently being aliphatic, cycloaliphatic or aromatic.
• decomposition accelerators reducing agents of peroxides or hydroperoxides
• tertiary amines and / or reducing agents containing salts of transition metals such as iron, cobalt or manganese carboxylates or vanadium.
• photoinitiators examples include benzoins, benzoin ethers, acetophenones, benziles, benzil ketals, anthraquinones, acylphosphine oxides, alpha-hydroxyketones, phenylglyoxylates, alpha-aminoketones, benzophenones, thioxanthones, xanthones, derivatives of quinoxaline and triazine compounds.
• the photoinitiator can be chosen from 2-methylanthraquinone, 2-ethylanthraquinone, 2-chloroanthraquinone, 2-benzylanthraquinone, 2-t-butylanthraquinone, 1, 2-benzo-9, 10-anthraquinone, benziles, benzoins, benzoin ethers, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, alpha-methylbenzoin, alpha-phenylbenzoin, Michler's ketones, acetophenones, benzophenones, benzophenone, 4,4'-bis- (diethylamino) benzophenone, acetophenone, 2,2-diethoxyacetophenone, 4-ethoxyacetophenone, 4-ethoxyacetophenone , thioxanthone, diethyl thioxanthone, 1, 5-aceton
• composition according to the invention comprises 0.5 to 10% by weight of component H) relative to the weight of all of the components A) to I).
• composition according to the invention can comprise a component I).
• the composition can comprise a mixture of components I).
• Component I) is an additive.
• additives include antioxidants, light stabilizers, light absorbers, polymerization inhibitors, defoamers, antistatic agents, leveling agents, dispersants (wetting agents, surfactants), slip agents, promoters adhesion agents, lubricants, pigments, dyes, fillers, chain transfer agents, rheological agents (thixotropic, thickener), mattifying agents, opacifying agents, impact resistance agents, waxes and any other agent commonly used in compositions inks, coatings, sealants, adhesives, castings, ink plates and 3D printing.
• composition according to the invention comprises 0 to 30% by weight of component I) relative to the weight of all components A) to I).
• composition according to the invention comprises:
• component A - 5 to less than 50%, in particular 10 to 40%, more particularly 15 to 30%, of component A);
• component B - 10 to 75%, in particular 15 to 70%, more particularly 20 to 60%, of component B);
• component F - 5 to 80%, in particular 8 to 55%, more particularly 15 to 40%, of component F);
• component G - 0 to 30%, in particular 0 to 20%, of component G
• component I - 0 to 30% of component I); the% being% by weight relative to the weight of all components A) to I).
• the composition does not comprise any compound other than the compounds A) to I).
• the weight of all components A) to I) can represent 100% of the weight of the composition.
• the total weight of components A) and C) represents less than 50% of the weight of all components A) to I).
• the total weight of components A) and B) represents 30 to 90%, in particular 35 to 85%, more particularly 40 to 80%, more particularly still 40 to 75%, of the weight of all components A) to H).
• the total weight of components A) and B) represents 40 to 90%, in particular 50 to 90%, more particularly 60 to 90%, more particularly still 70 to 90%, more particularly 80 at 90%, by weight of all components A) to H).
• the mass ratio between components A) and B) can in particular be from 0.1 to 5, in particular 0.2 to 2, more particularly 0.3 to 1.5, more particularly 0.4 to 1, even more particularly 0.5 to 0.8.
• the mass ratio between components A) and B) ranges from 0.1 to 1, in particular 0.1 to 0.8, more particularly 0.1 to 0.7, more particularly 0.1 to 0.6, still more particularly 0.2 to 0.6.
• the mass ratio of the components A) to F) can in particular be adjusted so that the Tg of the composition is such that the final product has good mechanical properties and optionally a flexible and / or elastomeric character.
• the composition according to the invention has a Tg of 0 to 30 ° C, in particular of 5 to 25 ° C.
• the Tg can be measured according to the method described below.
• the mass ratio of components A) to F) can be adjusted so that the composition has a suitable viscosity depending on the intended application.
• the composition according to the invention has a viscosity at 50 ° C of 1 to 20 mPa.s, in particular 5 to 15 mPa.s.
• composition according to the invention can in particular be a composition of ink, coating, mastic, adhesive, molding, ink plate or a composition for 3D printing.
• the composition according to the invention is a composition for 3D printing.
• composition according to the invention can in particular be used to obtain a crosslinked object and a 3D object according to the methods described below.
• the process for the manufacture of a crosslinked product comprises crosslinking the composition according to the invention.
• the composition can be crosslinked by exposing the composition to radiation and / or by heating the composition and / or by subjecting the composition to an oxidation-reduction reaction. More particularly, the composition can be crosslinked by exposing it to UV, near UV, visible, infrared or near infrared rays or to an electron beam.
• the composition can be applied to a substrate or poured into a mold before being crosslinked.
• the obtained crosslinked product can be an ink, a coating, a sealant, an adhesive, a molded material, an ink plate or a 3D object.
• the crosslinked product can be a 3D object.
• the 3D object can in particular be obtained with a method comprising printing a 3D object using the composition according to the invention.
• the method may in particular be a method of printing a 3D object continuously or layer by layer.
• the method according to the invention can be implemented in most 3D printing techniques.
• the process may in particular be a 3D tank or inkjet printing process.
• the process can in particular be a 3D printing process in which the composition according to the invention is contained in a tank and selectively cured (either in a plane or in space) by light-activated polymerization.
• This process is described in particular in the ISO 52900 (2015) standard.
• This process includes the various selective polymerization techniques induced by scanning a light beam (stereolithography - SLA), projection of light images (Digital light Processing - DLP) or exposure to light patterns from a screen.
• LCD liquid crystal device - LCD sometimes also called masked stereolithography - MSLA) or any other process exposing the resin to a light whose wavelength induces the initiation of polymerization at a specific location in the tank and limited only to this in law.
• the process can be a 3D printing process in which the composition according to the invention is sprayed in the form of drops or deposited in the form of a ribbon before being crosslinked under the effect of radiation.
• the composition can be sprayed on a support, on the previous layers or on a powdery substrate layer.
• a “layer by layer” 3D printing process comprises the following steps: a) depositing on a surface a first layer of composition according to the invention, b) crosslinking the first layer, at least partially, to obtain a first crosslinked layer, c) depositing on the first crosslinked layer, a second layer of composition according to the invention, d) crosslinking the second layer, at least partially, to obtain a second crosslinked layer, which is adhered to the first crosslinked layer; and e) repeating steps c) and d) the number of times necessary to obtain the 3D object.
• the crosslinking routes that can be used are those already described above with particular preference to the techniques of crosslinking by actinic radiation (UV, visible UV, near visible UV or EB electron beam) in the presence of a photoinitiator.
• composition according to the invention can also be used in processes for producing 3D objects according to a continuous process also called a CLIP method or process from its name in English: “Continuous Liquid Interface (or interphase) Product (or Printing) ".
• a continuous process also called a CLIP method or process from its name in English: “Continuous Liquid Interface (or interphase) Product (or Printing) ".
• This type of process is described in WO 2014/126830, WO 2014/126834 and WO 2014/126837 and in Tumbleston et al., “Continuous Liquid Interface Production of 3D Objects”, Science Vol. 347, Issue 6228, pp. 1349-1352 (March 20, 2015).
• the CLIP process proceeds by projecting a film or a continuous sequence of images by actinic radiation, for example UV, which can be generated, for example, by a digital imaging unit, through a window transparent to actinic radiation. and permeable to oxygen (inhibitor), located under a bath of the composition maintained in liquid form. A liquid interface below the (growing) article is maintained by the dead zone created above the window. The cured solid article is continuously withdrawn from the composition bath above the dead zone, which can be regenerated by introducing additional amounts of the composition into the bath to compensate for the amounts of composition cured and incorporated into the article by. growth.
• actinic radiation for example UV
• permeable to oxygen (inhibitor) located under a bath of the composition maintained in liquid form.
• a liquid interface below the (growing) article is maintained by the dead zone created above the window.
• the cured solid article is continuously withdrawn from the composition bath above the dead zone, which can be regenerated by introducing additional amounts of the composition into the bath to compensate for the amounts of composition
• a method of printing a 3D object using the composition according to the invention may comprise the following steps: a) providing a support (or printing plate) and an optically transparent element having a construction surface, the support and the construction surface defining between them a construction region, b) filling the construction region with the composition according to the invention, c) continuously or intermittently irradiating the construction region with actinic radiation, to form from of the composition a crosslinked composition, and d) continuously or intermittently, moving said support away from the construction surface to form the 3D object with the crosslinked composition.
• the continuous printing process can comprise the following steps: a) providing a support (or printing plate) and a stationary construction window, the construction window comprising a semi-permeable element, said semi-permeable element comprising a construction surface and a feed surface separate from the construction surface, the construction surface and the support defining between them a construction region, the feed surface being in liquid contact with a polymerization inhibitor, b) then and at the same time and / or sequentially, filling the construction region with a composition according to the invention, said composition being in contact with the printing plate, c) irradiating the build region through the build window to produce a solid cured region in the build region with a remaining liquid film layer made up of the composition, formed between the solid cured region and the build window, the polymerization of the liquid film being inhibited by polymerization inhibitor; and d) moving the print bed, to which the polymerized region is adhered, from the construction surface of the stationary window to create a construction region between the cured region and
• this process includes a step e) of repeating and / or continuing steps b) to d) to subsequently produce a polymerized region adhered to a previously polymerized region until the continuous or repeated deposition of polymerized regions. adhered to each other forms the targeted 3D object.
• the crosslinked product according to the invention is obtained by crosslinking the composition as defined above or according to the process described above.
• the crosslinked product can in particular be an ink, a coating, a mastic, an adhesive, a molded material, an inking plate or a 3D object, in particular the crosslinked product is a 3D object.
• the 3D objects obtained with the method according to the invention are advantageously sharp and easily peel off the plate. They may in particular exhibit good resistance to tearing and to folding.
• the 3D objects obtained are flexible and / or elastomeric. They can in particular exhibit an elongation before rupture of 120 to 250%.
• composition according to the invention can be used to obtain an ink, a coating, a sealant, an adhesive, a molded material, an inking plate or a 3D object. , in particular a 3D object.
• the invention also relates to the use of a mono (meth) acrylate comprising a 1,3-dioxolane ring in a composition for 3D printing.
• the mono (meth) acrylate comprising a 1,3-dioxolane ring can in particular correspond to component A) described above.
• the amount of component A) in the composition is advantageously from 5 to less than 50%, in particular 10 to 40%, more particularly 15 to 30%, by weight relative to the weight of the composition.
• the mono (meth) acrylate comprising a 1,3-dioxolane ring can advantageously be combined with one or more mono (meth) acrylate (s) distinct from the mono (meth) acrylate comprising a 1,3-dioxolane ring and / or with a or more oligomers comprising at least two (meth) acrylate groups and having a weight average molecular mass Mw greater than 700 g / mol.
• the mono (meth) acrylate (s) distinct from the mono (meth) acrylate comprising a 1,3-dioxolane ring can in particular correspond to component B) described above.
• the oligomer (s) comprising at least two (meth) acrylate groups and having a weight average molecular mass Mw greater than 700 g / mol can in particular correspond to component F) described above.
• the amount of component B) in the composition is advantageously 10 to 75%, in particular 15 to 70%, more particularly 20 to 60%, by weight relative to the weight of the composition.
• the total weight of components A) and B) represents 30 to 90%, in particular 35 to 85%, more particularly 40 to 80%, more particularly still 40 to 75%, of the weight of the composition.
• the total weight of components A) and B) represents 40 to 90%, in particular 50 to 90%, more particularly 60 to 90%, more particularly still 70 to 90%, more particularly 80 at 90%, by weight of the composition.
• the mass ratio between components A) and B) can in particular be from 0.1 to 5, in particular 0.2 to 2, more particularly 0.3 to 1.5, more particularly 0.4 to 1, even more particularly 0.5 to 0.8. In some cases, the mass ratio between components A) and B) ranges from 0.1 to 1, in particular 0.1 to 0.8, more particularly 0.1 to 0.7, more particularly 0.1 to 0.6, still more particularly 0.2 to 0.6.
• the amount of component F) in the composition is advantageously from 5 to 80%, in particular 8 to 55%, more particularly 15 to 40%, by weight relative to the weight of the composition.
• the composition can also comprise a component chosen from a component C), a component D), a component E), a component G), a component H), a component I) and their mixtures, as described above.
• the amount of component C) in the composition can be from 0 to less than 45%, in particular 1 to 40%, more particularly 2 to 20%, by weight relative to the weight of the composition.
• the total weight of components A) and C) can represent less than 50% of the weight of the composition.
• the amount of component D) in the composition can be 0 to 30%, in particular 0 to 20%, by weight relative to the weight of the composition.
• the amount of component E) in the composition can be 0 to 30%, in particular 0 to 20%, by weight relative to the weight of the composition.
• the amount of component G) in the composition can be 0 to 30%, in particular 0 to 20%, by weight relative to the weight of the composition.
• the amount of component H) in the composition can be 0.5 to 10% by weight based on the weight of the composition.
• the amount of component I) in the composition can be from 0 to 30% by weight relative to the weight of the composition.
• the composition does not comprise any compound other than the compounds A) to I).
• the weight of all components A) to I) can represent 100% of the weight of the composition.
• the glass transition temperature is obtained by Dynamic Mechanical Analysis (DMA).
• DMA Dynamic Mechanical Analysis
• the measurement of the storage (G ′) and loss (G ′′) moduli is carried out on a Rheometric Scientific R DA III device controlled by the RSI Orchestrator software, with a temperature rise from -40 ° C to 180 ° C at a speed of 3 ° C / min, by applying a rectangular torsional stress to a sample printed according to the printable object file of Figure 2 of dimension 80 * 10 * 4 mm (useful length between jaws adjustable between 1.5 and 4 cm, this value being taken into account in the calculation of the moduli by the software) with a typical strain rate of 0.05% (adjustable according to the response of the material) and a stress frequency of 1 Hz.
• DMA Dynamic Mechanical Analysis
• the samples have previously conditioned for at least 24 hours at 23 ° C +/- 2 ° C and with a relative humidity of 50% +/- 10%.
• the values of the storage moduli can be given at different temperatures, in particular at 25 ° C and at 150 ° C.
• the ratio G'VG ' is called the loss factor or tangent delta (tan delta).
• the Tg corresponds to the temperature for which the value of this tangent is maximum (Ta). This method makes it possible in particular to measure the glass transition temperature of polymeric materials for which direct measurement by DSC (differential scanning calorimetry) is impossible or difficult to determine.
• the surface tension is measured by the hanging drop method with a device
• the viscosity is measured at 50 ° C. with a Brookfield viscometer (Fungilab alpha series) equipped with a cylindrical mobile S27 rotating up to 100 rev / min.
• the temperature is kept constant with a temperature regulation system by circulating water.
• Weight average molecular mass The weight average molecular mass is determined by size exclusion chromatography (SEC) according to OECD (1996), Test No. 118: Determination of the Number-A verage Molecular Weight and the Molecular Weight Distribution ofPoiymers using Gel Permeation Chromatography, OECD Guidelines for the Testing of Chemicals, Section 1, OECD Publishing, Paris. The following conditions are used:
• the print quality of a 3D object is determined visually on a printed object according to the printable object file in Figure 4 and a score of 0 to 5 is assigned according to the following scale:
• Elongation and tensile stress are obtained on an object printed according to the printable object file of Figure 1 with a tensile test according to ISO 527-5A: 1993 with a tensile speed of 500 mm / min .
• Tear resistance is obtained on an object printed according to the object file printable of Figure 3 according to standard D624 type C, 2012 with a tensile speed of 500 mm / min.
• Hardness was measured on an object printed according to the printable object file of Figure 1 according to ISO 868: 2003 with an A Shore durometer. The measurements were taken after 5 seconds of contact between the measuring tip and the sample
• CN966 aliphatic urethane diacrylate having a weight average molecular mass of 7000 g / mol available from Arkema under the reference CN966H90 (commercial mixture containing 90% by weight of CN966 and 10% by weight of SR256 relative to the weight of the mixture )
• IPGA 2,2-dimethyl-1, 3-dioxolan-4-yl) methyl acrylate obtained by trans esterification reaction between isopropylidene glycerol (Augeo SL 191, Solvay) and methyl acrylate (Arkema), with a ratio 2 to 3 acrylate / alcohol molar, catalyzed with Zirconium acetylacetonate (Zr (AcAc) 4, Sachem).
• the trans-esterification reaction is carried out (8 h) by adding the catalyst to the reaction medium with mechanical stirring and by slightly reducing the pressure within the reactor in order to maintain a reaction temperature below 100 ° C.
• reaction by-product methanol
• methanol is extracted by reflux distillation of a methanol / methyl acrylate azeotrope.
• the residual methyl acrylate is removed by stripping at reduced pressure ( ⁇ 100 mbar, 1:30).
• the desired reaction product IPGA is purified by low pressure distillation ( ⁇ 15 mbar,
• SR506D isobornyl acrylate having a molecular mass of 208 g / mol sold under the reference SR506D by Arkema
• SR256 2 (2-ethoxyethoxy) ethyl acrylate having a molecular mass of 188 g / mol sold under the reference SR256 by Arkema
• TPO-L ethyl (2,4,6-trimethylbenzoyl) phenyl phosphinate marketed under the reference SpeedCure® TPO-L by Lambson
• compositions are prepared using the compounds detailed in the table below (the amounts are indicated in% by weight relative to the weight of the composition, the amount of CN966 corresponds to the actual amount of oligomer and the amount of SR256 corresponds to the quantity of monomer introduced by the commercial mixture CN966H90).
• the monofunctional monomers (IPGA, SR495B and / or SR506D) and the oligomer (CN966 mixed with SR256) are separately preheated to 65 ° C. With manual stirring, the oligomer is introduced into one of the monofunctional monomers (the most important in%) and homogenized. The rest of the monomers are then added to the mixture. The photo initiator (TPO-L or B PO) is introduced last. The temperature of the mixture is allowed to drop to room temperature (20-25 ° C).
• Example 2 3D Objects 3D objects were printed using the compositions of Example 1 according to the printable object file shown in Figures 1-4. The prints were made on a Photon model 3D printer (Anycubic LCD printer). The printing program used for each example is detailed in the table below (the adhesion layers are the layers in contact with the platform, also called “bottom layers”). The parts obtained after printing are subjected to a post- cooking under 12V LED lamp equipped with a conveyor bench with 10 passages at a speed of 5 m / min.
• compositions K049, K040, K048 and K054 according to the invention are of good quality and all the details of the model part are present. These articles also exhibit good elongation, a soft and pleasant feel as well as suitable mechanical properties. These objects are obtained with compositions comprising 40 to 90% by weight of component A) and of component B) relative to the weight of the composition and having a mass ratio between component A) and component B) of 0.2 to 0.6.
• compositions K022 and K023 according to the invention exhibit excellent elongation but are delaminated (part of the layers are missing). These objects are obtained with compositions comprising 40 to 90% by weight of component A) and of component B) relative to the weight of the composition and having a mass ratio between component A) and component B) of 1.4 to 2.0.
• component B) comprising at least 15% by weight of soft and hydrophilic monomer, such as polycaprolactone acrylate and 2 (2-ethoxyethoxy) ethyl acrylate, for example compared to the weight of component B), improves the quality of 3D printing of flexible and elastomeric objects.

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• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
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• Polyurethanes Or Polyureas (AREA)
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• 2019
  • 2019-12-31 FR FR1915759A patent/FR3105791B1/fr active Active
• 2020
  • 2020-12-22 EP EP20839046.8A patent/EP4084957A1/fr active Pending
  • 2020-12-22 US US17/789,305 patent/US20230073050A1/en active Pending
  • 2020-12-22 IL IL294245A patent/IL294245A/en unknown
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